Journal of Alloys and Compounds 741 (2018) 723e733

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Gd doping effect on impedance spectroscopy properties of sol-gel

prepared Pr0.5-xGdxSr0.5MnO3 (0
x
0.3) perovskites
A. Ben Jazia Kharrat a, *, M. Bourouina a, N. Moutia b, K. Khirouni b, W. Boujelben a
a
Laboratoire de Physique des Mat
eriaux, Facult
e des Sciences de Sfax, Universit
e de Sfax, B. P 1171, 3000, Sfax, Tunisia
b
Laboratoire de Physique des Mat
eriaux et des Nanomat eriaux appliqu  l’Environnement, Facult
ee a e des Sciences de Gab
es, Universit
e de Gab
es, cit
e
Erriadh, 6079, Gab
es, Tunisia

a r t i c l e i n f o a b s t r a c t

Article history: The electrical and dielectric properties of Pr0.5-xGdxSr0.5MnO3 (0
x
0.3) manganites prepared by the
Received 29 July 2017 conventional sol-gel method have been studied in a wide range of temperature [80e320 K] and fre-
Received in revised form quency [40e107 Hz] using impedance spectroscopy technique. DC conductivity (sDC) results show that
6 January 2018
for x ¼ 0, 0.1 and 0.2, the samples present a semiconductor behavior in the temperature range of the
Accepted 16 January 2018
study. For x ¼ 0.3, a semiconductor-metal transition is observed at 280 K. sDC shows also a decrease in
the conductivity with the increase of Gd doping. The calculated activation energies are Gd content
dependent. AC conductivity results were analysed using Drude model in the metallic region and by the
Keywords:
Pr0.5Sr0.5MnO3
Jonsher power law in the semiconductor one. The Niquist plots for x ¼ 0.2 and x ¼ 0.3 obeys at Cole-Cole
Gd-doping model. The impedance spectra were fitted by an adequate equivalent circuit involving two contributions
Impedance spectroscopy attributed to grains and grain boundaries associated with an inductance. Such a result reveals a corre-
Electrical properties lation between electrical and magnetic properties of Gd-doped manganites. In addition, grain-boundary
Drude model resistance shows a major contribution at higher temperature. High dielectric constants are obtained in
Dielectric properties particular at low frequencies. Dielectric loss is analyzed through the Giuntini theory with which we have
calculated the energy required for charge carriers to hope over the potential barriers.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction properties were obtained in various doped manganites [4e6]. In

addition, colossal dielectric constants were obtained in structures
Recently, with the discovery of important electrical and dielec- such as La0.7Sr0.25Na0.05Mn0.9Ti0.1O3 [7] and Pr0.7Ca0.3Mn1xNixO3
tric properties of perovskites, an increasing interest is given to this [8].
type of materials characterized by their low cost and easy prepa- We are interested in this study to half doped manganites which
ration methods. The most interesting challenge is to select the are characterized by equal amounts of Mn3þ and Mn4þ ions. The
adequate structures which provide high electrical response, high most peculiar character of these materials is the CMR effect
dielectric constants and low dielectric loss, in particular at micro- compared to MCE. We have chosen the Pr0.5Sr0.5MnO3 system
wave frequencies. Perovskite manganites with the general formula which is one of the most studied manganite materials up till now
Te1-xExMnO3 (where Te is a trivalent rare earth ion and E is a [9e11]. Doping with gadolinium can enhance MCE properties since
divalent or trivalent alkaline-earth ion) were at the basic of large this element is known as the best candidate for magnetic refrig-
field of investigations in last decencies thanks to the technological eration [12].
applications that they offer [1e3]. The most recognized physical In our laboratory, the magnetotransport properties of Pr0.5-
properties are the colossal magnetoresistance (CMR) and the xGdxSr0.5MnO3 (x ¼ 0.0 and 0.1) compounds have been reported
magnetocaloric effect (MCE) which are explained, in the manganite [13]. On the other hand, recent studies have demonstrated that
compounds, in the basis of the double-exchange interactions be- perovskite compounds such as GdCr1-xFexO3 (0
x < 1) and
tween Mn3þ and Mn4þ ions. Besides, interesting electrical Gd0.05MnxZn0.95-xO (x ¼ 0.03, 0.05 and 0.07) show colossal dielec-
tric constant [14,15]. Magnetic properties of Gd-based manganites
were widely investigated but their electrical and dielectric prop-
* Corresponding author. erties using impedance spectroscopy are not studied as we know.
E-mail address: [email protected] (A. Ben Jazia Kharrat). Indeed, the advantage of this method is its strong ability to separate

https://doi.org/10.1016/j.jallcom.2018.01.236
0925-8388/© 2018 Elsevier B.V. All rights reserved.
724 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733

the bulk, grain boundary and electrode contributions. xGdxSr0.5MnO3 (x ¼ 0; 0.1, 0.2 and 0.3) compounds. The obtained
In the present study, we report the effect of gadolinium on the lines are fine and intense and signature of a good crystallization of
temperature and frequency dependence of electrical and dielectric our samples. Using the Rietveld refinement technique with the
properties of polycrystalline Pr0.5-xGdxSr0.5MnO3 (x ¼ 0, 0.1, 0.2 and Fullprof program [17], we have deduced that the parent sample
0.3) compounds prepared by sol-gel route. crystallizes in the tetragonal structure with I4/mcm space group but
the doped ones crystallize in the distorted orthorhombic structure
2. Experimental details with Pbnm space group.
The cell lattice parameters, the unit cell volume V, the average
Polycrystalline samples of Pr0.5-xGdxSr0.5MnO3 (x ¼ 0, 0.1, 0.2 〈MneO〉 bond length, the average angle 〈MneOeMn〉, the average
and 0.3) were prepared using the conventional sol-gel method [16]. ionic radius in A-site 〈rA〉 and the cationic disorder in A-site s2 for
We have used as precursors Pr6O11, Gd2O3, SrCO3 and MnO2 up to all our compounds, deduced from the refinement results, were
99.9% purity in the desired proportion. The phase purity and the summarized in Table 1.
single phase nature of our compounds were confirmed by X-ray Since the Pr3þ and Gd3þ ions have the same valence, the Mn3þ/
powder diffraction (XRD) using (CuKa) radiation source. For elec- Mn4þ ratio is not affected. In Fig. 1-b, we have plotted the evolution
trical measurements, the samples, prepared as pellets, with a of V and 〈rA〉 as a function of the Gd doping rate. It is clear that the
thickness of 1 mm were used. In both side of each pellet, a thin substitution of Pr by Gd leads to an increase of the unit cell volume
silver layer was deposited in order to obtain ohmic contacts. An in contrary to what obtained in a previous work where Pr0.5-
Agilent 4294A analyzer was used to provide the conductance xGdxSr0.5MnO3 (x ¼ 0, 0.05 and 0.1) samples were prepared by
measurements over a wide range of frequency (40 Hze10 MHz). the conventional solid state route. The 〈rA〉 values decreases due to
The amplitude of the applied alternating signal is of 50 mV. A liquid the difference between the ionic radius of Pr ð rPr3þ ¼ 1:179 AÞ and
nitrogen cooled VPF-100 cryostat of Janis Corporation is used in Gd ð rGd3þ ¼ 1:107 AÞ [18]. In our samples prepared by sol-gel route,
order to provide the variation of temperature from 80 to 320 K. the increase of the Gd content inside the structure causes an in-
crease of the average 〈MneO〉 bond length and the decrease of the
3. Results and discussion average angle 〈MneOeMn〉 (listed in Table 1) and leads to a tilting
of the MnO6 octahedrons. As a result, the unit cell volume increases.
3.1. Structural properties

Fig. 1-a shows the XRD patterns for all our studied Pr0.5- 3.2. DC conductivity analysis

Fig. 2-a gives the temperature dependence of the DC electrical

conductivity sDC for Pr0.5-xGdxSr0.5MnO3 (x ¼ 0; 0.1, 0.2 and 0.3)
compounds. These results were obtained from AC measurements at
low frequencies (40 Hz). As seen, samples with x ¼ 0, 0.1 and 0.2
exhibit a semiconducting behavior in the whole explored temper-
ature range. For x ¼ 0.3, a transition from a semiconductor to a
metallic behavior is observed at TSM ¼ 280 K. It is important to
signal the important conductivity values obtained in these struc-
tures. On other hand, sDC decreases when the Gd content increases
over the explored temperature range. Thus, increasing Gd content
enhances the resistivity values as reported in a previous work [13].
Such a result confirms that Gd doping enhances the electronic
localization certainly due to the increase of the cationic disorder
which limits the double exchange mechanism between Mn3þ and
Mn4þ ions. It is worth noticing that an abrupt increase of conduc-
tivity is observed for the sample corresponding to
x ¼ 0.2 at T ¼ 100 K which can be related to a sudden release of
trapped charges by the defects introduced by the cationic disorder,
at such temperature.
Fig. 2-b shows the evolution of Ln (sDCT) versus the reverse of
absolute temperature for all studied compounds. Usually, these
curves obey, at high temperatures, to Arrhenius law given by:

Table 1
The principle refinement results: the cell lattice parameters, the unit cell volume,
the average ionic radius in A-site 〈rA〉 and the cationic disorder in A-site s2 for Pr0.5-
xGdxSr0.5MnO3 (0
x
0.3) compounds.

Sample x¼0 x ¼ 0.1 x ¼ 0.2 x ¼ 0.3

a (Å) 5.397(6) 5.442(7) 5.439(0) 5.433(1)

b (Å) 5.397(6) 5.470(4) 5.465(2) 5.441(5)
pffiffiffi
c= 2 (Å) 5.492(5) 5.402(6) 5.411(6) 5.455(3)
V (Å3) 226.299 227.486 227.501 228.087
〈MneO〉(Å) 1.949 1.968 1.9835 2.015
〈MneOeMn〉 ( ) 164.45 152.75 150.98 147.75
Fig. 1. (a) XRD patterns and (b) evolution of the unit cell volume and the cationic
s2 (103 Å2) 4.29 5.70 7.01 8.21
disorder s2 with the Gd doping concentration x in the Pr0.5-xGdxSr0.5MnO3
〈rA〉 (Å) 1.245 1.237 1.230 1.223
(0
x
0.3) compounds.
 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733 725

reveals that the AC conductivity plots can be divided in two parts. In

the first one, the conductivity is frequency independent. A disper-
sion of the conductivity with frequency behind a specific frequency
us ¼ 2pfs is observed in the second part. For the compounds with
x ¼ 0 and x ¼ 0.1, the conductivity decreases with frequency for
higher values than fs for the all explored temperature range. Such
evolution is a signature of metallic behaviour. For the compounds
with x ¼ 0.2 and x ¼ 0.3, the conductivity increases with the fre-
quency for low temperature like an insulator behaviour and it fol-
lows a metallic behaviour at high temperature. Such evolution is
usually encountered in this type of materials.
Fig. 4 shows the frequency dependence of the conductivity for
Pr0.5-xGdxSr0.5MnO3 (0
x
0.3) compounds measured at T ¼ 80 K.
The metallic character observed for x ¼ 0 and 0.1 is completely
suppressed by doping the parent sample with a 20% of Gd and the
dielectric behaviour is accentuated for x ¼ 0.3.
By examining the electrical response of compounds (x ¼ 0 and
0.1), we can observe that they exhibit a metallic behaviour. Usually
in such materials, the conductivity is governed by electron super-
exchange between metallic ions through oxygen. This charge car-
rier transfer is very sensitive to the presence of defects, lattice
distortions, polarization, etc … which induces an energy barrier to
overcome [20]. In samples prepared by solid state reaction a
semiconductor behavior is usually encountered. In fact, the sol gel
route for sample preparation is expected to introduce less con-
centration of defects, so charge carriers can hope easily from one
site to another. This can explain the metallic behavior obtained in
Pr0.5-xGdxSr0.5MnO3 (x ¼ 0 and 0.1) compounds. In contrary, the
doped samples Pr0.3Gd0.2Sr0.5MnO3 (PGSMO1) and
Pr0.2Gd0.3Sr0.5MnO3 (PGSMO2) present two different behaviours: a
semiconductor regime at low temperatures and a metallic one at
high temperatures with a semiconductor-to-metallic transition
estimated at 100 K and 120 K for PGSMO1 and PGSMO2 respec-
tively. These two compounds will be the subject of a fine analysis in
the following parts of this paper.
Usually, in nanostructure materials having a metallic behaviour,
Fig. 2. (a) DC Conductivity spectra and (b) evolution of sDCT vs (1000/T) for Pr0.5- the AC conductivity can be described by the Drude-Smith model
xGdxSr0.5MnO3 (0
x
0.3) compounds. [21]. In our case, the conductivity sAC of all our prepared samples
follows the classical Drude model [22]. According to this model, sAC
is well described by the following expression:

sDC :T ¼ s0 :ekT
Ea
(1) sDC
sAC ðuÞ ¼   (2)
1 þ u2 t2s
where s0 is a constant, Ea is the activation energy and k the
Boltzmann constant. It can be seen that these plots are linear over a ts represents the relaxation time describing the electron-phonon
wide temperature range, confirming the thermally activated small scattering. From the fit shown in Fig. 3 of sAC(u) using relation
polaron hopping mechanism (SPH) [19]. The activation energies Ea (2), we have plotted the temperature evolution of ts for all our
are obtained from the slope of Ln(sDC.T) vs 1000/T curves. At high compounds. As shown in Fig. 5, the relaxation time increases with
temperatures, these values are 31, 35, 36 and 67 meV for x ¼ 0, 0.1, temperature which confirms the metallic behaviour of our samples
0.2 and 0.3 respectively. For x ¼ 0.3, the activation energy was in the studied range of temperature. This metallic character is
calculated in the temperature range of the insulator behavior. observed in other materials such as Li0.5Mn0.5Fe2O4-d [23] and Pr0.8-
The low value of activation energies confirms that the mobility
xBixSr0.2MnO3 [24].
of the charge carriers is due to a hopping mechanism dominated by In order to determine the AC activation energies, we have
the motion of electrons through the structure. The increase of Ea plotted Ln(ts) as a function of 1000/T relative to our compounds
values with Gd content confirms that the increase of electronic (the curves are not shown). The calculated values are 16, 17 and
localization makes the hoping of carriers from one site to another 18 meV for x ¼ 0, 0.1 and 0.2 respectively. These values are lower
harder. The introduced disorder by Gd substitution enhances than those obtained from DC measurements. Such difference is due
considerably the potential barrier that charge carrier has to over- to the fact that in the AC conductivity, the electronic jumps be-
come when x increase from 0.2 to 0.3 and this explains the strong tween localized states are frequency dependent [25]. An increase in
decrease of the conductivity. frequency is accompanied by an increase of the absorbed energy
[26] and this enhances the electronic jumps and reduces the acti-
3.3. AC conductivity analysis vation energy [27]. For x ¼ 0.3, we have a metallic behaviour at high
temperature and it is inappropriate to model the corresponding
The frequency dependence of the AC conductivity sAC for all our curve by a thermal activated process.
compounds at different temperatures is given in Fig. 3. This figure It is worth noticing that the semiconductor character observed
726 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733

Fig. 3. Frequency dependence of the conductivity at different temperatures for Pr0.5-xGdxSr0.5MnO3 (0
x
0.3) compounds: x ¼ 0.0 (a), x ¼ 0.1 (b), x ¼ 0.2 (c) and x ¼ 0.3 (d).

Fig. 4. Frequency dependence of the conductivity for Pr0.5-xGdxSr0.5MnO3 (0
x
0.3)

compounds at T ¼ 80 K.
Fig. 5. Temperature dependence of the relaxation time ts obtained from relation (2)
for Pr0.5-xGdxSr0.5MnO3 (0
x
0.3) compounds: x ¼ 0.0 (a), x ¼ 0.1 (b), x ¼ 0.2 (c) and
at low temperatures means that the conductivity is governed by x ¼ 0.3 (d). The insets show the evolution of Ln(tsT) vs 1000/T.
localized short-range of hopping charge carriers. But at high tem-
peratures, the transition from semiconductor to metallic behaviour
can be explained by the additional thermal energy together with polarizability in the structure and depends only on temperature
electron scattering effects [23]. and s describes the degree of interaction between ions and the host
In the semiconductor region and for PGSMO1 and PGSMO2 lattice. It depends on both frequency and temperature. The sudden
samples, the AC conductivity, at low temperatures, is well increase in AC conductivity with frequency indicates the presence
described by the Jonscher power law [28]: of hopping type mechanism in electrical conduction in these
compounds.
sAC ðuÞ ¼ sDC þ Aus (3) Relation (3) has been used to fit the AC results for the doped
samples PGSMO1 and PGSMO2. The parameters sDC and s were
where u is the angular frequency, A describes the strength of gathered in Table 2. For both samples, the s values exceed 1.
 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733 727

Table 2
The best fitting results of the conductivity sDC obtained from experimental data as a
function of frequency using the Jonscher's power law for Pr0.5-xGdxSr0.5MnO3
(0
x
0.3) compounds.

T (K) sDC A s R2 uh
(103 S cm1) (104 rd/s)

Pr0.3Gd0.2Sr0.5MnO3
80 4.06 5.68 1016 1.750 0.999 2214
90 6.53 3.68 1014 1.494 0.996 3385
95 8.42 1.15 1013 1.405 0.992 5405
Pr0.2Gd0.3Sr0.5MnO3
80 0.312 3.48 1014 1.445 0.998 772
90 0.725 3.22 1015 1.598 0.998 1271
95 0.976 1.56 1015 1.645 0.999 1483
100 1.67 1.20 1015 1.665 0.999 1965
105 2.49 8.23 1016 1.685 0.999 2553
110 3.56 2.49 1016 1.746 0.989 3424
115 4.9 2.26 1018 2.013 0.952 4155

According to Funke [29], if the value of s is less than 1, the electron

jump takes place between two distant sites and the case s > 1
corresponds to a jump of charge carriers between neighbouring
sites.
By studying the variation of the exponent s as a function of the
temperature for the two compounds, it can be seen that for the
PGSMO1 sample, s decreases with increasing temperature as
observed in disordered materials [30], whereas for the second
sample, s increases as the temperature increases.
Then, two models can be proposed to describe the conduction
mechanism in these samples: the correlated barrier hopping (CBH)
model for PGSMO1 and the non-overlapping small polaron
tunnelling (NSPT) model for PGSMO2.
For the CBH model, the conduction is ensured by polaron hop-
ping process over the Coulomb barrier which separates two defect
Fig. 6. Temperature dependence of the frequency exponent s and (1-s) for PGSMO1 (a)
centers and the exponent s can be described by the formula that
and PGSMO2 (b) compounds.
follows [31]:

6kT the density of free carriers.

s¼1 (4)
Wm þ kTlnðut0 Þ We have shown on the curve of Fig. 6-b the temperature
dependence of s and (1-s) for the PGSMO2 sample. WH can be
where Wm represents the binding energy required to move a calculated using the slope of the line (1-s) as a function of tem-
charge carrier from one site to another and t0 is the characteristic perature. The obtained value of WH is 37 meV.
relaxation time, generally in the order of an atom vibrational At fixed temperature, the crossover frequency from DC to
period. The expression (4) can be also simplified when dispersive AC conductivity values is done at a hopping frequency uh
Wm [kTlnðut0 Þ [32]: given by the following expression [34]:

6kT
s¼1 (5)
Wm s 1=s
Then, the plot of (1-s) vs temperature shown in Fig. 6-a, gives us uh ¼ DC
(8)
A
the average binding energy Wm of the PGSMO1 compound which is
evaluated as 22 meV. In Fig. 7, we have plotted the sAC data scaled by a Ghosh's model
Therefore, the most suitable model that describes the conduc- [35].
tion mechanism in the second sample is the non-overlapping small
polaron tunnelling model. According to this model, the s parameter
 
is given by Ref. [33]: sAC ðuÞ u
¼f (9)
sDC uh
4
s¼1þW (6) Accordingly, for the two studied compounds, the curves show a
kT
H
 Lnðut0 Þ
perfect overlap for all temperatures indicating that the relaxation
In this expression, WH represents the polaron hopping energy. dynamics of the charge carriers is temperature independent [36].
For larger values of WH
, relation (6) can be reduced to: The variation of Ln(uh) with temperature for the doped samples
kT
is shown in the inset of Fig. 7. As we can see, these curves follow the
4 kT Arrhenius model and the calculated activation energies are 36 and
s¼1þ (7)
WH 43 meV for PGSMO1 and PGSMO2 respectively which suppose a
more localization of charge carriers due to the increase of Gd
s increases with increasing temperature indicating an increase in content.
728 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733

Fig. 7. Plot of (sAC/sDC) versus (u/uh) at different temperatures for PGSMO1 (a) and
PGSMO2 (b) compounds. The inset shows the temperature evolution of ln(uh) and the
calculated activation energies.

3.4. Impedance spectroscopy

Impedance spectroscopy is a powerful characterization method

used to separate the contributions of various processes especially
grain and grain boundary effects [37]. This technique is widely used
to model a structure by an equivalent circuit having the same AC
characteristics. We have determined the Nyquist plots (imaginary
part of complex impedance Z00 vs real part of complex impedance
Z0 ) of the doped samples Pr0.3Gd0.2Sr0.5MnO3 and
Pr0.2Gd0.3Sr0.5MnO3 at low temperatures. Impedance data for Fig. 8. Complex impedance spectrum (Nyquist plot) with electrical equivalent circuit
PGSMO1 and PGSMO2 compounds at different temperatures are for: Pr0.3Gd0.2Sr0.5MnO3 sample (a) Pr0.2Gd0.3Sr0.5MnO3 sample at 80 K
T
100 K (b)
and Pr0.2Gd0.3Sr0.5MnO3 sample at 105 K
T
115 K where the inset shows the
depicted in Fig. 8. By analyzing these curves, we can see that they
inductive loop (c). The solid line represents the fit of the experimental data.
are characterized by the presence of two semicircles centred below
the real axis, signature of Cole-Cole model [38]. It is well known
that the higher frequency semicircle corresponds to grain response semicircles decreases when the temperature increases, a signature
and the lower one to the grain boundary. Nevertheless, a problem of activated conduction mechanism [39]. In addition, their centers
persists in the modelling of structures 1 and 2 towards high fre- are depressed below the real axis, which indicates that the relax-
quencies. This problem has been overcome by adding an induc- ation process is non-Debye type [40].
tance L in the circuit. The presence of this inductance can be The simulation of impedance complex data allows us to define
explained by the existence of a non-homogeneity distribution of the equivalent circuit relative to each compound at different tem-
the electrically polarized ions inside the grains. In the studied peratures. The adequate equivalent circuit for the PGSMO1 sample
temperature range, we can see that the radius of experimental is consisted of a series combination R þ Lþ(Rg//CPEg), where Rg is
 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733 729

the resistance of bulk (inset of Fig. 8-a). The presence of a unique Nyquist plots, reported in Fig. 8, show a good agreement be-
semicircle in this structure can be attributed to bulk grain [41]. The tween experimental (scatter) and simulated curves (solid lines).
impedance of fractal capacitance CPEg is given by Ref. [42]: It is worth noticing that the Niquist plots for PGSMO1 and
PGSMO2 show a low-frequency inductive loop which increases
1 with temperature. This phenomenon was observed in metal/yttria
ZCPEg ¼ (10)
Q ðjuÞag stabilized zirconia electrodes and was attributed to the presence of
adsorbed species [43]. In our samples, the inductive effect can be
In this expression, Q is the capacitance value of the CPEg
attributed to the presence of gadolinium in the structure.
impedance and ag (0<ag < 1) describes the deviation from Debey's
For the PGSMO2 sample, and for 105
T
115 K, the inductive
model.
effect is more accentuated as seen in the second inset of Fig. 8-c.
Then, the real and imaginary parts of the total impedance of this
The change in the electronic model relative to this sample may
circuit are determined according to the following expressions:
originate from the increase of the L value with increasing
a p temperature.
0 Rg 1 þ Rg Q uag cos 2g
Z ¼Rþ a p2  a p2 (11) Fig. 9 indicates the frequency dependence of the real part Z0 of
1 þ Rg Q uag cos 2g þ Rg Q uag sin 2g the impedance at different temperatures referred to PGSMO1 and
PGSMO2 samples. In the low frequency range, Z0 shows higher
and values which decreases with temperature. For high frequency
a p values, Z0 presents lower values which may due to the release of
00 R2g Q uag sin 2g space charge polarization [44] and correlated with the increase of
Z ¼ a p2  a p2  Lu (12)
AC conductivity in this region. The Z0 spectra is well fitted by
1 þ Rg Q uag cos 2g þ Rg Q uag sin 2g
relation (11) for PGSMO1 and by relations (13) and (15) for
For the PGSMO2 sample, and in the temperature range PGSMO2.
80
T
100 K, The adequate equivalent circuit is illustrated in the The frequency dependence of the imaginary part Z00 of the
inset of Fig. 8-b where CPEgb is the fractal capacitance relative to impedance at various temperatures is shown in Fig. 10. These
grain boundaries. curves were simulated using relation (12) for sample PGSMO1 and
In this case, the real and imaginary parts of the total impedance equations (14) and (16) for sample PGSMO2 (solid lines). For each
are given by the expressions: compound, the plots show peaks which shift to higher frequencies
when the temperature increases showing a thermally activated
Rg relaxation phenomenon. A broad peak is observed in all Z00 which
Z0 ¼ R þ  2
1 þ Rg Cg u can be attributed to the existence of multiple relaxation times in
h  i the two studied compounds. We can notice, in addition, that the
a p
Rgb 1 þ Rgb Q uagb cos gb2 maximum of these peaks decreases with increasing temperature
þ     
a p 2 a p 2 and merges at high frequencies. Such behavior is a signature of an
1 þ Rgb Q uagb cos gb2 þ Rgb Q uagb sin gb2 accumulation of space charge polarization effect in our compounds
(13) which occurs at higher temperatures and lower frequencies [45]. By
analyzing both curves of Z0 and Z00 , we can notice that when the
and frequency increases, Z00 increases up to a particular value at which a
sudden decrease in Z0 value is detected. Such trend confirms the
00 R2g Cg u existence of a relaxation phenomenon in PGSMO1 and PGSMO2
Z ¼  2 structures which occurs at a frequency noted fr. Using the relation
1 þ R g Cg u
  t ¼ 1/(2pfr), the relaxation time t is calculated for the
R2gb Q uagb sin ap
2 Pr0.2Gd0.3Sr0.5MnO3 sample and plotted vs 1000/T in the inset of
þ  2     Lu Fig. 10. The obtained activation energy corresponding to non-Debey
a a p a p 2
1 þ Rgb Q u gb cos 2 gb
þ Rgb Q uagb sin gb2 relaxation is Ea ¼ 46 meV which is in good agreement with that
(14) obtained from Ln(uh) vs temperature curve.
The activation energies obtained from DC and AC measurements
For 105
T
115 K, The adequate equivalent circuit is shown in in the PGSMO1 and PGSMO2 compounds are different which sug-
the inset of Fig. 8-c. As a consequence, the real and imaginary parts gests that the charge carriers in the semiconductor region have to
of the total impedance of this circuit can be written as: overcome different energy barrier while conducting and relaxing.
For the Pr0.2Gd0.3Sr0.5MnO3 sample, the evolution of Rg and Rgb
Rg Rgb
Z0 ¼  2 þ  2 (15) at different temperatures can be analysed using the adiabatic small
1 þ Rg Cg u 1 þ Rgb Cgb u polaron hopping model [46] described by:
 
Ea
and Rg;gb ¼ R0;1 T a exp (17)
kT
00 R2g Cg u R2gb Cgb u In this expression, Ea is the activation energy, R0 and R1 are
Z ¼  2 þ  2  L u (16)
1 þ R g Cg u 1þ R C u
constants related to the polaron hopping concentration and
gb gb

The extracted parameters, for all these circuits are summarized Table 3
in Table 3 (for sample PGSMO1) and Table 4 (for sample PGSMO2). The equivalent circuit parameters obtained for the Pr0.3Gd0.2Sr0.5MnO3 sample.
It is worth noticing that Rgb present higher values due to accu-
T(K) L (106H) R(U) Rg(U) Q (1010F) ag
mulation of defects at the vicinity of grain boundaries such as
dangling bonds and a non-stoichiometric distribution of oxygen 80 2.00 30.3 130 3.63 0.942
90 1.94 37.6 61.5 7.27 0.984
[39].
730 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733

Table 4
The equivalent circuit parameters obtained for the Pr0.2Gd0.3Sr0.5MnO3 compound.

T(K) R(U) L(106H) Rg(U) Cg(1010F) Rgb(U) Qgb(109F) agb Cgb(1010F)

80 101 1.66 162 7.26 1870 0.939 0.922

90 83.4 1.79 150 5.64 676 0.877 0.951
95 77.7 1.82 131 5.30 409 0.88 0.964
100 71.8 1.87 117 4.52 205 0.759 0.997
105 2.42 107 1.26 160 5.36
110 2.11 86.2 5.63 102 4.38
115 2.92 66.4 3.26 75.6 3.89

Fig. 10. Frequency dependence of the imaginary part (Z00 ) of the impedance at different
temperatures for (a) Pr0.3Gd0.2Sr0.5MnO3 and (b) Pr0.2Gd0.3Sr0.5MnO3 (The inset of this
figure shows the temperature dependence of the relaxation time). The solid line
Fig. 9. Frequency dependence of the real part (Z0 ) of the impedance at different represents the fit of the experimental data.
temperatures for: Pr0.3Gd0.2Sr0.5MnO3 (a) and Pr0.2Gd0.3Sr0.5MnO3 (b) compounds. The
solid line represents the fit of the experimental data.

Rgb
diffusion and a ¼ 1 in the case of adiabatic hopping. b¼ (18)
Rg þ Rgb
Fig. 11 shows the evolution of Ln(Rg/T) and Ln(Rgb/T) against
the inverse of absolute temperature. The calculated activation en- As depicted in Fig. 12, the blocking factor decreases with
ergies are 83 and 27 meV respectively. These values, compared to increasing temperature. Since b can be related to the fraction of
those obtained from DC conduction analysis and from Ln(t) vs charge carriers blocked at the grain boundaries, we can say that the
1000/T for PGSMO2 sample, shows that the effect of the grain charge carriers become freer as temperature increases and the total
boundaries dominates at low temperatures, whereas the effect of conductivity tends to the conductivity of grains.
the grains manifests towards the high temperatures. This behavior
indicates an increase of the mobility of charge carriers with rise in 3.5. Dielectric properties
temperature which causes an increase in the conduction process.
In order to study the grain boundaries effect on the total con- In the studied samples, the complex permittivity is defined as:
00 00
ductivity of Pr0.2Gd0.3Sr0.5MnO3 sample, we have calculated the ε* ðf Þ ¼ ε0 ðf Þ  jε ðf Þ where ε0 and ε are respectively the real and the
blocking factor b expressed as [47]: imaginary parts of ε* . ε0 and ε00 are calculated using the following
relation [48]:
 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733 731

Fig. 11. Variation of Ln(Rg/T) and Ln(Rgb/T) as a function of 1000/T for

Pr0.2Gd0.3Sr0.5MnO3 compound.

e
ε* ¼ (19)
juε0 SZ *
S is the area of electrodes, e the thickness of the sample and
ε0 denotes the permittivity of the vacuum.
Fig. 13-a shows the frequency evolution of ε0 at some repre-
sentative temperatures for the PGSMO2 sample. As clearly seen,
very higher values of permittivity can be obtained with this type of
perovskites which can give higher values of capacities which is
beneficial for technological applications. The ε0 values increase with
temperature but decrease with frequency. It is well known that at
low frequencies and temperatures, all mechanisms of polarization
(interfacial polarization, dipoles, ions and electrons) can exist in the
structure. All polarization mechanisms tend to follow the applied
electric field. Consequently, a maximum of the real dielectric Fig. 13. Frequency dependence of: ε’ (a) and Ln (ε00 ) (b) at some representative tem-
permittivity is obtained at low frequencies and temperatures. As peratures for Pr0.2Gd0.3Sr0.5MnO3 compound. The inset shows the evolution of the
frequency increases, the polarized dipoles present in these struc- maximum barrier height versus temperature relative to the same compound.

tures cannot follow the orientation of the applied electric field and
the permittivity decreases strongly. An increase in temperature
conductivity and leads to the reduction of interfacial polarization.
causes an increase in the disorder of the dipoles and makes the
As a result, ε0 values decrease with frequency and temperature.
jump of charge carriers easier which causes an increase in the
In Fig. 13-b, we report the evolution of the complex permittivity
ε00 as a function of frequency at different temperatures for the
PGSMO2 sample. The plotted curves show straight lines whose
slopes are close to 1, which means that the DC conduction
mechanism is predominant in both doped compounds. The ε00 plots
can be analyzed with the equation given by Giuntini theory [49]:

00
4 m
ε ðuÞ ¼ ðε0  ε∞ Þ2p2 Nðne=ε0 Þ3 kT tm
0 WM u (20)
In this expression, N and n represent respectively the number of
the localized states and the number of charge carriers able to cross
the potential barrier, ε0 and ε∞ are the values of the static
(determined at low frequency) and high frequency dielectric con-
stant, t0 is the relaxation time and WM denotes the energy required
for carriers to jump over the potential barrier.
Relation (19) can be expressed as:

00
ε ðuÞ ¼ aðTÞ: um (21)

Fig. 12. Thermal evolution of the blocking factor b for Pr0.2Gd0.3Sr0.5MnO3 compound. where
732 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733

properties of La0.7Sr0.25Na0.05Mn0.9Ti0.1O3 ceramics, Physica B 440 (2014)

m ¼ 4kB T=WM (22) 118e123.
[8] R. Jemai, R. M'nassri, A. Selmi, H. Rahmouni, K. Khirouni, N. ChnibaBoudjada,
A. Cheikhrouhou, Composition dependence of physical properties in
a(T) depends only on temperature and m describes the interaction Pr0.7Ca0.3Mn1xNixO3, J. Alloy. Comp. 693 (2017) 631e641.
between the different electrical dipoles. Using the latter relations [9] W. Boujelben, M. Ellouze, A. Cheikh-Rouhou, J. Pierre, J.C. Joubert, Effect of
(20) and (21), we can calculate at each temperature the value of WM quenching on magnetoresistance properties in the Pr0.5Sr0.5MnO3 perovskite
manganite, J. Solid State Chem. 165 (2002) 375e380.
for the PGSMO2 sample. The evolution of WM with temperature is [10] A.K. Pramanik, A. Banerjee, Phase separation and the effect of quenched dis-
shown in the inset of Fig. 13-b. As we can see, WM increases slightly order in Pr0.5Sr0.5MnO3, J. Phys. Condens. Matter 20 (2008), 275207.
due to the disorder caused by the increase of temperature. In [11] L. Chen, Y. Chen, Y. Ma, G. Lian, Y. Zhang, G. Xiong, Influence of epitaxial
growth on phase competition in Pr0.5Sr0.5MnO3 films, J. Magn. Magn. Mater.
addition, we can remark that WM increases linearly with temper-
324 (2012) 1189e1192.
ature (slope 0.325). The same slope was obtained in our previous [12] M. Bourouina, A. Krichene, N. Chniba Boudjada, W. Boujelben, Phase separa-
work with Pr0.8-xBixSr0.2MnO3 samples [24]. tion and magnetocaloric effect in Pr0.5-xGdxSr0.5MnO3 system, J. Alloy. Comp.
680 (2016) 67e72.
[13] M. Bourouina, A. Krichene, R. Thaljaoui, M. Pekała, W. Boujelben, Effect of
4. Conclusions gadolinium doping on the structural and electrical properties of Pr0.5-
xGdxSr0.5MnO3 (x-0.0-0.1) manganites, J. Supercond. Nov. Magn. 28 (2015)
2743e2750.
Pr0.5-xGdxSr0.5MnO3 (0
x
0.3) manganites are prepared by [14] J. Shanker, K. Venkataramana, B. Vittal Prasad, R. Vijaya Kumar, D. Suresh
sol gel route at T ¼ 800  C. All studied samples are single phase. Babu, Influence of Fe substitution on structural and electrical properties of Gd
Rietveld refinement shows that the parent sample crystallizes in orthochromite ceramics, J. Alloy. Comp. 732 (2018) 314e327.
[15] Santanu Das, Sukhen Das, Soumyaditya Sutradhar, Enhanced dielectric
the tetragonal structure with I4/mcm space group but the doped
behavior and ac electrical response in Gd-Mn-ZnO nanoparticles, J. Alloy.
ones crystallise in the orthorhombic structure with Pbnm space Comp. 726 (2017) 11e21.
group. The obtained results confirm that the electrical properties of [16] H. Brunckova, L. Medvecky, J. Briancin, K. Saksl, Influence of hydrolysis con-
ditions of the acetate sol-gel process on the stoichiometry of PZT powders,
our compounds are Gd content, temperature and frequency
Ceram. Int. 30 (2004) 453e460.
dependent. The DC conductivity data show that all compounds [17] H.M. Rietveld, Appl. Cryst. 2 (1965) 65e71.
exhibit a semiconductor behavior but for x ¼ 0.3, a semiconductor- [18] R.D. Shannon, Revised effective ionic radii and systematic studies of inter-
metal transition is observed at TSM ¼ 280 K. In addition the con- atomic distances in halides and chaleogenides, Acta Cryst. A32 (1976)
751e767.
ductivity decreases with the increase of doping content. In the [19] N.F. Mott, E.A. Davis, Electronic Process in Non-crystalline Materials, Clar-
semiconductor region, the AC conductivity measurements follow endon Press, Oxford, 1979.
the Jonsher power law indicating the presence of a hopping con- [20] R.N. Bhowmik, Abdul Gaffar Lone, Dielectric properties of a-Fe1.6Ga0.4O3
oxide: a promising magneto-electric material, J. Alloy. Comp. 680 (2016)
duction process. The temperature dependence of the exponent s 31e42.
suggests that the conduction mechanism is described by NSPT [21] N.V. Smith, Classical generalization of the Drude formula for the optical
model. The impedance spectra, which show a clear deviation from conductivity, Phys. Rev. B 64 (2001), 155106.
[22] K. Lee, S. Cho, S.H. Park, A.J. Heeger, C.W. Lee, S.H. Lee, Metallic transport in
Debey's model, are fitted by an equivalent circuit which involves polyaniline, Nature 441 (04705) (2006) 65e68.
two contributions associated with the grains and the grain [23] R.N. Bhowmik, G. Vijayasri, Study of microstructure and semiconductor to
boundaries. High dielectric constants, which depend on both metallic conductivity transition in solid state sintered Li0.5Mn0.5Fe2O4d spinel
ferrite, J. Appl. Phys. 114 (2013), 223701e223701-6.
temperature and frequency, are obtained. All these results confirm
[24] A. Ben Jazia Kharrat, S. Moussa, N. Moutiaa, K. Khirouni, W. Boujelben,
that the electrical and dielectric properties of the prepared samples Structural, electrical and dielectric properties of Bi-doped Pr0.8-xBixSr0.2MnO3
are strongly dependent on temperature and frequency. manganite oxides prepared by sol-gel process, J. Alloy. Comp. 724 (2017)
389e399.
The obtained results are critical for understanding the behavior
[25] F. Yakuphanoglu, E. Evin, M. Okutan, The dielectrical and alternating current
of Gd-polycrystalline manganites used on magnetic refrigeration. conductivity properties of 40Cuþ20Coþ40Y2O3 ceramic, Physica B 382 (2006)
Introducing Gd in Pr0.5Sr0.5MnO3 reduces the conductivity and 285e289.
makes appear a magnetic property through the existence of an [26] T.A. Abdel-Baset, A. Hassen, Dielectric relaxation analysis and Ac conductivity
of polyvinyl alcohol/polyacrylonitrile film, Physica B 499 (2016) 24e28.
inductance in the electric equivalent circuit. The study of com- [27] H.E. Atyia, Electrical conductivity and dielectric relaxation of bulk
pounds with higher Gd content and of the magnetic properties will Se70Bi(30 x)Tex, x ¼ (0, 15) chalcogenide glasses, J. Non-Cryst. Solids 391
be interesting. (2014) 83e90.
[28] A.K. Jonscher, Dielectric Relaxation in Solids, Chelsea Dielectric Press, London,
1983.
Acknowledgements [29] K. Funke, Prog. J. Solid State Chem. 22 (1993) 111e195.
[30] S.R. Elliot, Philos. Mag. B 37 (1978) 553e560.
[31] B.K. Chaudhuri, K. Chaudhuri, K.K. Som, Concentration and frequency de-
This work has been supported by the Tunisian Ministry of pendences of A.C. conductivity and dielectric constant of iron-bismuth oxide
Higher Education and Scientific Research. glassesdII, J. Phys. Chem. Solid. 50 (1989) 1149e1155.
[32] K.H. Mahmoud, F.M. Abdel-Rahim, K. Atef, Y.B. Saddeek, Dielectric dispersion
in lithiumebismuth-borate glasses, Curr. Appl. Phys. 11 (2011) 55e60.
References [33] S.R. Elliott, A.c. conduction in amorphous chalcogenide and pnictide semi-
conductors, Adv. Phys. 36 (1987) 135e217.
[1] N.Q. Minh, Ceramic fuel cells, Am. Ceram. Soc. 76 (1993) 563e588. [34] A. Ben Hafsia, N. Rammeh, M. Farid, M. Khitouni, Electrical conductivity and
[2] N. Khare, D.P. Singh, H.K. Singh, A.K. Gupta, P.K. Siwach, O.N. Srivastava, dielectric study of LaBaFe0.5Zn0.5MnO6-d compound, Ceram. Int. 42 (2016)
Preparation and study of silver added La0.67Ca0.33MnO3 film, J. Phys. Chem. 3673.
Solid. 65 (2004) 867e870. [35] B. Louati, F. Hlel, K. Guidara, Dielectric and ac ionic conductivity investigations
[3] Z.C. Xia, S.L. Yuan, W. Feng, L.J. Zhang, G.H. Zang, J. Tang, L. Liu, D.W. Liu, in the monetite, J. Alloy. Comp. 486 (2009) 299e306.
Q.H. Zheng, L. Chen, Z.H. Fang, S. Liu, C.Q. Tang, Magnetoresistance and [36] A. Pan, A. Ghosh, Correlation of relaxation dynamics and conductivity spectra
transport properties of different impurity doped La0.67Ca0.33MnO3 composite, with cation constriction in ion-conducting glasses, Phys. Rev. B 66 (2002)
Solid State Commun. 127 (2003) 567e572. 12301e12307.
[4] H. Rahmouni, A. Dhahri, K. Khirouni, The effect of tin addition on the electrical [37] B. Behera, P. Nayak, R.N.P. Choudhary, Structural and impedance properties of
conductivity of Sn-doped LaBaMnO3, J. Alloy. Comp. 591 (2014) 259e262. KBa2V5O15 ceramics, Mater. Res. Bull. 43 (2008) 401e410.
[5] H. Rahmouni, B. Cherif, M. Baazaoui, K. Khirouni, Effects of iron concentrations [38] A.K. Jonscher, Analysis of the alternating current properties of ionic conduc-
on the electrical properties of La0.67Ba0.33Mn1-xFexO3, J. Alloy. Comp. 575 tors, J. Mater. Sci. 13 (1978) 553e562.
(2013) 5e9. [39] M. Khelifi, R. M’nassri, A. Selmi, H. Rahmouni, K. Khirouni, N. Chniba Boudjada,
[6] H. Rahmouni, B. Cherif, R. Jemai, A. Dhahri, K. Khirouni, Europium substitution A. Cheikhrouhou, Investigation of magnetic and transport properties of
for lanthanum in LaBaMnO e the structural and electrical properties of PrCa(MnCo)O prepared by solid state process, J. Magn. Magn. Mater. 423
La0.7xEuxBa0.3MnO3 perovskite, J. Alloy. Comp. 690 (2017) 890e895. (2017) 20e26.
[7] S.E.L. Kossi, F.I.H. Rhouma, J. Dhahri, K. Khirouni, Structural and electric [40] H. Nefzi, F. Sediri, H. Hamzaoui, N. Gharbi, Electric conductivity analysis and
 A. Ben Jazia Kharrat et al. / Journal of Alloys and Compounds 741 (2018) 723e733 733

dielectric relaxation behavior of the hybrid polyvanadate (H3N(CH2)3NH3) organic semiconductor: Alizarin, Phys. B 388 (2007) 118e123.
[V4O10], Mater. Res. Bull. 48 (2013) 1978e1983. [46] A. Banerjee, S. Pal, E. Rozenberg, B.K. Chaudhuri, Adiabatic and non-adiabatic
[41] A.K. Behera, N.K. Mohanty, B. Behera, P. Nayak, Impedance properties of small-polaron hopping conduction in La1xPbxMnO3þd (0.0
x
0.5)-type ox-
0.7(BiFeO3)e0.3(PbTiO3) composite, Adv. Mater. Lett. 4 (2013) 141e145. ides above the metalesemiconductor transition, J. Phys. Condens. Matter 13
[42] A.K. Jonscher, The interpretation of non-ideal dielectric admittance and (2001) 9489.
impedance diagrams, Phys. Status Solidi (a) 32 (1975) 665e676. [47] M.J. Verkerk, B.J. Middelhuis, A.J. Burggraaf, Solid State Ionics 6 (1982)
[43] R.J. Aaberg, R. Tunold, M. Mogensen, R.W. Berg, R. Odegrd, Morphological 159e170.
changes at the interface of the nickel-yitria stabilized zirconia point electrode, [48] A. von Hippel, Dielectrics and Waves, John Wiley and Sons, New York, 1954.
J. Electrochem. Soc. 145 (1998) 2244e2252. [49] J.C. Giuntini, J.V. Zanchetta, D. Jullien, R. Eholie, P. Houenou, Temperature
[44] M. Ganguli, M. Harish Bhat, K.J. Rao, Lithium ion transport in Li2SO4-Li2O-B2O3 dependence of dielectric losses in chalcogenide glasses, J. Non-Cryst. Solids 45
glasses, Phys. Chem. Glasses 40 (1999) 297e304. (1981) 57e62.
[45] K.P. Chandra, K. Prasad, R.N. Gupta, Impedance spectroscopy study of an